Cathodic Zn underpotential deposition: an evitable degradation mechanism in aqueous zinc-ion batteries

Shaohua Zhu; Yuhang Dai; Jinghao Li; Chumei Ye; Wanhai Zhou; Ruohan Yu; Xiaobin Liao; Jiantao Li; Wei Zhang; Wei Zong; Ruwei Chen; Guanjie He; Dongliang Chao; Qinyou An

doi:10.1016/j.scib.2022.08.023

Cathodic Zn underpotential deposition: an evitable degradation mechanism in aqueous zinc-ion batteries

Sci Bull (Beijing). 2022 Sep 30;67(18):1882-1889. doi: 10.1016/j.scib.2022.08.023. Epub 2022 Aug 20.

Authors

Shaohua Zhu¹, Yuhang Dai², Jinghao Li¹, Chumei Ye³, Wanhai Zhou⁴, Ruohan Yu¹, Xiaobin Liao⁵, Jiantao Li¹, Wei Zhang⁶, Wei Zong⁶, Ruwei Chen⁶, Guanjie He⁷, Dongliang Chao⁸, Qinyou An⁹

Affiliations

¹ State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China.
² State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China; Christopher Ingold Laboratory, Department of Chemistry, University College London, London WC1H 0AJ, UK; Electrochemical Innovation Laboratory, Department of Chemical Engineering, University College London, London WC1E 7JE, UK.
³ Department of Materials Science and Metallurgy, University of Cambridge, Cambridge CB3 0FS, UK.
⁴ Laboratory of Advanced Materials, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, and School of Chemistry and Materials, Fudan University, Shanghai 200433, China.
⁵ State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070, China.
⁶ Christopher Ingold Laboratory, Department of Chemistry, University College London, London WC1H 0AJ, UK.
⁷ Christopher Ingold Laboratory, Department of Chemistry, University College London, London WC1H 0AJ, UK; Electrochemical Innovation Laboratory, Department of Chemical Engineering, University College London, London WC1E 7JE, UK. Electronic address: [email protected].
⁸ Laboratory of Advanced Materials, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, and School of Chemistry and Materials, Fudan University, Shanghai 200433, China. Electronic address: [email protected].
⁹ State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China. Electronic address: [email protected].

PMID: 36546302
DOI: 10.1016/j.scib.2022.08.023

Abstract

Aqueous zinc-ion batteries (AZIBs) are promising for large-scale energy storage, but their development is plagued by inadequate cycle life. Here, for the first time, we reveal an unusual phenomenon of cathodic underpotential deposition (UPD) of Zn, which is highly irreversible and considered the origin of the inferior cycling stability of AZIBs. Combining experimental and theoretical simulation approaches, we propose that the UPD process agrees with a two-dimensional nucleation and growth model, following a thermodynamically feasible mechanism. Furthermore, the universality of Zn UPD is identified in systems, including VO₂//Zn, TiO₂//Zn, and SnO₂//Zn. In practice, we propose and successfully implement removing cathodic Zn UPD and substantially mitigate the degradation of the battery by controlling the end-of-discharge voltage. This work provides new insights into AZIBs degradation and brings the cathodic UPD behavior of rechargeable batteries into the limelight.

Keywords: Aqueous battery; Degradation mechanism; Underpotential deposition; Zinc-ion battery; Zn metal deposition.